CN112374496B - Preparation method of biomass porous carbon material based on iodine simple substance pore-forming agent and electrochemical energy storage application of biomass porous carbon material - Google Patents
Preparation method of biomass porous carbon material based on iodine simple substance pore-forming agent and electrochemical energy storage application of biomass porous carbon material Download PDFInfo
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- 239000003575 carbonaceous material Substances 0.000 title claims abstract description 68
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 title claims abstract description 44
- 229910052740 iodine Inorganic materials 0.000 title claims abstract description 44
- 239000011630 iodine Substances 0.000 title claims abstract description 44
- 239000002028 Biomass Substances 0.000 title claims abstract description 31
- 239000000126 substance Substances 0.000 title claims abstract description 26
- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 17
- 238000012983 electrochemical energy storage Methods 0.000 title claims abstract description 15
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 239000011148 porous material Substances 0.000 claims abstract description 12
- 238000000034 method Methods 0.000 claims description 17
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 claims description 17
- 238000003756 stirring Methods 0.000 claims description 16
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 13
- 239000000843 powder Substances 0.000 claims description 12
- 239000011259 mixed solution Substances 0.000 claims description 10
- 229920002472 Starch Polymers 0.000 claims description 9
- 239000008107 starch Substances 0.000 claims description 9
- 235000019698 starch Nutrition 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 7
- 229910052799 carbon Inorganic materials 0.000 claims description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 6
- 235000010333 potassium nitrate Nutrition 0.000 claims description 6
- 239000004323 potassium nitrate Substances 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 5
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 claims description 5
- 239000002253 acid Substances 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- 235000002906 tartaric acid Nutrition 0.000 claims description 5
- 239000011975 tartaric acid Substances 0.000 claims description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- 239000000243 solution Substances 0.000 claims description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 3
- 238000010000 carbonizing Methods 0.000 claims description 3
- 238000000227 grinding Methods 0.000 claims description 3
- 239000012535 impurity Substances 0.000 claims description 3
- 230000007935 neutral effect Effects 0.000 claims description 3
- 229910017604 nitric acid Inorganic materials 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 239000010453 quartz Substances 0.000 claims description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
- 238000009210 therapy by ultrasound Methods 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 2
- 229910052786 argon Inorganic materials 0.000 claims description 2
- 239000011261 inert gas Substances 0.000 claims description 2
- 235000006408 oxalic acid Nutrition 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 abstract description 17
- 239000008103 glucose Substances 0.000 abstract description 17
- 239000003463 adsorbent Substances 0.000 abstract description 2
- 239000003054 catalyst Substances 0.000 abstract description 2
- 239000000463 material Substances 0.000 description 9
- 238000003763 carbonization Methods 0.000 description 8
- 238000012360 testing method Methods 0.000 description 4
- 238000001069 Raman spectroscopy Methods 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 230000004913 activation Effects 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- FVAUCKIRQBBSSJ-UHFFFAOYSA-M sodium iodide Chemical compound [Na+].[I-] FVAUCKIRQBBSSJ-UHFFFAOYSA-M 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 229920000557 Nafion® Polymers 0.000 description 2
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 239000003990 capacitor Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000002484 cyclic voltammetry Methods 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- ORXJMBXYSGGCHG-UHFFFAOYSA-N dimethyl 2-methoxypropanedioate Chemical compound COC(=O)C(OC)C(=O)OC ORXJMBXYSGGCHG-UHFFFAOYSA-N 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 239000004744 fabric Substances 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- TXKAQZRUJUNDHI-UHFFFAOYSA-K bismuth tribromide Chemical compound Br[Bi](Br)Br TXKAQZRUJUNDHI-UHFFFAOYSA-K 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 125000003636 chemical group Chemical group 0.000 description 1
- 238000011278 co-treatment Methods 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000000840 electrochemical analysis Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 125000002791 glucosyl group Chemical group C1([C@H](O)[C@@H](O)[C@H](O)[C@H](O1)CO)* 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 229910052987 metal hydride Inorganic materials 0.000 description 1
- 238000000053 physical method Methods 0.000 description 1
- AVTYONGGKAJVTE-OLXYHTOASA-L potassium L-tartrate Chemical compound [K+].[K+].[O-]C(=O)[C@H](O)[C@@H](O)C([O-])=O AVTYONGGKAJVTE-OLXYHTOASA-L 0.000 description 1
- 239000001472 potassium tartrate Substances 0.000 description 1
- 229940111695 potassium tartrate Drugs 0.000 description 1
- 235000011005 potassium tartrates Nutrition 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000000750 progressive effect Effects 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 235000009518 sodium iodide Nutrition 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000002336 sorption--desorption measurement Methods 0.000 description 1
- 238000000859 sublimation Methods 0.000 description 1
- 230000008022 sublimation Effects 0.000 description 1
- ZSDSQXJSNMTJDA-UHFFFAOYSA-N trifluralin Chemical compound CCCN(CCC)C1=C([N+]([O-])=O)C=C(C(F)(F)F)C=C1[N+]([O-])=O ZSDSQXJSNMTJDA-UHFFFAOYSA-N 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/30—Active carbon
- C01B32/312—Preparation
- C01B32/318—Preparation characterised by the starting materials
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/30—Active carbon
- C01B32/312—Preparation
- C01B32/342—Preparation characterised by non-gaseous activating agents
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/30—Active carbon
- C01B32/312—Preparation
- C01B32/342—Preparation characterised by non-gaseous activating agents
- C01B32/348—Metallic compounds
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/24—Electrodes characterised by structural features of the materials making up or comprised in the electrodes, e.g. form, surface area or porosity; characterised by the structural features of powders or particles used therefor
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/32—Carbon-based
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Power Engineering (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The invention relates to a preparation method of a porous carbon material, in particular to a preparation method of a biomass porous carbon material based on a novel iodine simple substance pore-forming agent and electrochemical energy storage application thereof, and belongs to the field of preparation of porous carbon materials. The invention provides a novel pore-forming agent for glucose biomass. According to the invention, iodine simple substance is used as a pore forming agent to carry out pore forming on the glucose-based biomass carbon material, so that the specific surface area of the glucose-based biomass carbon material is increased, the porous carbon material with high specific surface area is prepared, and the obtained porous carbon material can be applied to the fields of electrochemical energy storage, adsorbents, catalysts and the like.
Description
Technical Field
The invention relates to a preparation method of a porous carbon material, in particular to a preparation method of a biomass porous carbon material based on a novel iodine simple substance pore-forming agent and electrochemical energy storage application thereof, and belongs to the field of preparation of porous carbon materials.
Background
Porous carbon materials play an important role in many aspects such as energy storage and environmental protection. The method for preparing the porous carbon material by activating and carbonizing the biomass is an environment-friendly and economic method. At present, the methods for biomass activation pore-forming mainly include physical methods and chemical methods. Wherein, the physical activation method firstly pyrolyzes the biomass into carbon material and then carries out CO treatment in a certain atmosphere2、NH3、H2Etching with gas such as O, air and the like; the chemical activation method comprisesRefers to the reaction of a carbon source with a chemical reagent during pyrolysis, and common chemical reagents include: KOH, NaOH, H3PO4、KNO3、ZnCl2And the like. The biomass material containing glucose, such as starch, is abundant in reserves and can be used as an excellent biomass material, the iodine simple substance can be combined with glucose, and the blue change of the starch and the iodine is the reason for the combination of the iodine simple substance and the glucose. By utilizing the combination characteristic of the iodine simple substance and glucose-containing materials such as starch and the like, the iodine simple substance is sublimated at high temperature to etch the carbon material, and a large number of micropores and mesopores are left in the biomass carbon material, so that the specific surface area of the glucose-containing biomass carbon material is increased. At present, no patent or article reports that the porous carbon material is prepared by utilizing the characteristic of combining iodine simple substance with glucose-containing materials such as starch.
Disclosure of Invention
The invention aims to provide a preparation method of a biomass porous carbon material based on a novel iodine simple substance pore-forming agent, which aims to solve the problems in the prior art.
The technical scheme adopted by the invention for solving the technical problems is as follows:
a preparation method of a biomass porous carbon material based on a novel iodine simple substance pore-forming agent sequentially comprises the following steps:
s1: dissolving a carbon source in water;
s2: adding an iodine source into the solution obtained in the last step, heating to 90 ℃, and stirring for dissolving;
s3: adding tartaric acid into the mixed solution obtained in the last step, and stirring for dissolving;
s4: adding potassium nitrate into the mixed solution obtained in the last step, and stirring for dissolving;
s5: drying the mixed solution obtained in the last step at the temperature of 80-180 ℃ for 8-48 h;
s6: grinding the porous foamy solid obtained in the last step into powder, putting the powder into a quartz crucible, and carbonizing the powder by raising the temperature to 600-1200 ℃ at a temperature rise rate of 2-20 ℃/min under the protection of inert atmosphere;
s7: and (3) fully stirring the powder obtained in the last step in dilute acid, removing impurities in the carbon material by ultrasonic waves, washing the carbon material to be neutral by water, and drying the carbon material to obtain the porous carbon material.
In steps S3 and S4, tartaric acid and potassium nitrate were used as the surfactant and the pore-forming agent, respectively.
The invention provides a novel pore-forming agent for glucose biomass. According to the invention, iodine simple substance is used as a pore forming agent to carry out pore forming on the glucose-based biomass carbon material, so that the specific surface area of the glucose-based biomass carbon material is increased, the porous carbon material with high specific surface area is prepared, and the obtained porous carbon material can be applied to the fields of electrochemical energy storage, adsorbents, catalysts and the like.
Preferably, in step S1, the carbon source is soluble starch, glucose or biomass containing glucose.
Preferably, in step S2, the iodine source is elemental iodine or a compound containing iodine. Further, the iodine-containing compound includes potassium iodide or sodium iodide.
Preferably, in step S6, the carbonization time is 60 to 180 min.
Preferably, in step S6, the inert gas is argon or nitrogen.
Preferably, in step S7, the diluted acid is 0.1-3M hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid or oxalic acid, the stirring treatment time is 0.5-6 h, the ultrasonic treatment time is 0.5-6 h, the oven temperature is 80-180 ℃, and the drying time is 8-48 h.
The biomass porous carbon material based on the novel iodine simple substance pore-forming agent is prepared by the preparation method.
The application of the biomass porous carbon material based on the novel iodine simple substance pore-forming agent in the aspects of electrochemical energy storage and the like is provided.
The principle of the invention is that 1 iodine simple substance is combined with 6 glucose molecules in starch, then sublimation reaction is carried out at high temperature, and more micropores and mesopores are produced in the carbon material, as shown in formula (1); combining tartaric acid with potassium nitrate to generate potassium tartrate, serving as a surfactant, and foaming starch at 120 ℃ to form a porous foam-like material, as shown in formula (2); excess potassium nitrate etches the carbon material at high temperature, creating a porous structure, as shown in equation (3). The schematic diagram of the preparation of the porous carbon material is shown in FIG. 1.
I2+6n(C6H10O5)→2n(C18H30O5I) (1)
HOOCCHOHCHOHCOOH+KNO3→HOOCCHOHCHOHCOOK+HNO3 (2)
C+2KNO3→2KNO2+CO2↑ (3)
Compared with the prior art, the method has the advantages that the iodine simple substance is used as the pore forming agent to perform pore forming on the glucosyl biomass carbon material, so that the specific surface area of the carbon material is effectively increased, and when the iodine simple substance is added, the specific surface area of the porous carbon material reaches 2989m2 g-1Relative to 2139m when no iodine is added2 g-1The improvement is 39.7%.
Drawings
Fig. 1 is a schematic diagram of the preparation principle of the porous carbon material.
FIG. 2 shows adsorption and desorption curves (a), Raman curves (b) and pore size distribution curves (c) (d) of porous carbon materials prepared according to examples 1, 2, 3 and 4 and using different iodine contents.
FIG. 3 shows adsorption-desorption curves (a), pore size distribution curves (b), Raman curves (c) and X-ray diffraction curves (d) of porous carbon materials prepared in examples 1, 5 and 6 using different carbonization temperatures.
FIG. 4 shows the electrochemical energy storage characteristics of the porous carbon material I-PCs-0.14-1000 prepared in example 1 under the two-electrode test condition: (a) I-PCs-0.14-1000 in 1.5M HCl and 1.5M HCl +0.05M BiBr3Cyclic voltammogram of (5 mV/s); (b) I-PCs-0.14-1000 in 1.5M HCl and 1.5M HCl +0.05M BiBr3Constant current charge-discharge curve (2A/g); (c) I-PCs-0.14-1000 in 1.5M HCl +0.05M BiBr3(iv) cyclic voltammograms at different current densities of (2A/g, 5A/g, 8A/g, 10A/g, 15A/g and 20A/g); (d) typical energy storage devices (electrochemical capacitors, lead-acid batteries, nickel-metal hydride batteries, lithium ion batteries) and I-PCs-0.14-1000 at 1.5M HCl +0.05M BiBr3Energy density versus power density plot in (1).
Detailed Description
The technical solution of the present invention will be further specifically described below by way of specific examples. It is to be understood that the practice of the invention is not limited to the following examples, and that any variations and/or modifications may be made thereto without departing from the scope of the invention.
In the present invention, all parts and percentages are by weight, unless otherwise specified, and the equipment and materials used are commercially available or commonly used in the art. The methods in the following examples are conventional in the art unless otherwise specified.
Sample characterization method
The specific surface area was measured by BET (Micromeritics Tristar 3000), the physical properties of the carbon material were measured by Raman (Thermal Dispersive Spectrometer), and X-ray diffraction (XRD, Bruker D8) using Cu Kα1Radiation
The structural characteristics of the carbon material were tested under 1.6kW (40kV,40mA) conditions.
Preparing an electrode material in an electrochemical test process: preparing slurry from porous carbon material and 0.05% nafion ethanol solution, stirring, and dripping on carbon cloth (loading amount of 4 mg/cm)2) And putting the sample into a vacuum drying oven at 80 ℃, drying for 1 hour, and then testing the electrochemical energy storage property of the sample by adopting an electrochemical workstation (CHI760E, Shanghai Chenghua).
Example 1:
a pore-forming method based on iodine simple substance comprises the following specific steps:
s1: adding 3g of soluble starch (national chemical group chemical reagent Co., Ltd.) into 30ml of deionized water, and stirring for dissolving;
s2: adding 0.14g of iodine simple substance into the mixed solution, heating to 90 ℃, and stirring for dissolving;
s3: adding 2.5g tartaric acid into the mixed solution, and stirring for dissolving;
s4: adding 3.4g of potassium nitrate into the mixed solution, and stirring for dissolving;
s5: putting the mixed solution into a large beaker, and then putting the beaker into a 120 ℃ oven for treatment for 24 hours;
s6: grinding the porous foamy solid obtained in the step into powder, putting the powder into a quartz crucible, and treating the powder for 90min at 1000 ℃ under the protection of nitrogen inert atmosphere, wherein the heating rate is 10 ℃/min.
S7: and putting the powder obtained in the step into 1M HCl, stirring for 2h, performing ultrasonic treatment for 2h to remove impurities in the carbon material, washing the carbon material to be neutral by using deionized water, and then putting the carbon material into a 100 ℃ oven for drying, wherein the obtained sample is named as I-PCs-0.14-1000.
Examples 2, 3 and 4 were provided to further investigate the influence of the amount of iodine added on the physical properties such as the pore structure of the carbon material.
Example 2:
this example is the same as example 1 except that the amount of iodine used was 0g, and the porous carbon material thus prepared was named I-PCs-0 to 1000.
Example 3:
this example is the same as example 1 except that the amount of iodine used was 0.07g and the porous carbon material was named I-PCs-0.07-1000.
Example 4:
this example is the same as example 1 except that the amount of iodine used is 0.28g and the porous carbon material prepared is named I-PCs-0.28-1000.
Specific surface junctions and electrochemical energy storage properties of the carbon material prepared by using elementary iodine with different contents are shown in table 1 and fig. 2.
Table 1: the specific surface area, pore volume and specific capacity of the samples prepared by different iodine contents.
aThe specific surface area and volume of the micropores were obtained from t-plot method.bThe specific capacity is 1M H2SO4The electrolyte is obtained by adopting a three-electrode test at the concentration of 1A/g.
From examples 1, 2, 3 and 4, it can be seen that when the iodine content is 0.14g, the prepared material has the largest specific surface area and the highest specific capacity, and the molar ratio of glucose to iodine is 6:1, which is just up to 6 glucose fixed number ratio of 1 iodine.
In order to further explore the influence of different carbonization temperatures on the specific surface area, the conductivity, the specific capacity and other properties of the material, examples 5 and 6 were carried out.
Example 5:
this example is the same as example 1 except that the carbonization temperature in step 6 was changed to 700 ℃ to prepare a porous carbon material named I-PCs-0.14-700.
Example 6:
this example is the same as example 1 except that the carbonization temperature in step 6 was changed to 850 deg.C, and a porous carbon material was prepared and named I-PCs-0.14-850.
The specific surface junction and electrochemical energy storage properties of the carbon materials prepared using different carbonization temperatures are shown in table 2 and fig. 3.
Table 2: the specific surface area, pore volume and specific capacity of the samples prepared by different carbonization temperatures.
aThe specific surface area and volume of the micropores were obtained from t-plot method.
From examples 1, 5 and 6, it can be seen that the materials prepared have the largest specific surface area and the lowest resistivity at a carbonization temperature of 1000 ℃.
Application example:
the prepared porous carbon material is applied to electrochemical energy storage of the active electrolyte enhanced super capacitor. Sample I-PCs-0.14-1000 was mixed with nafion at a volume concentration of 0.05%,preparing slurry, and dropping the slurry on a carbon cloth, respectively adding 1.5M HCl and 1.5M HCl +0.05M BiBr3Testing electrochemical energy storage characteristics. In active electrolyte, at 2A g-1The specific capacity reaches 1216F g at the current density of-1The energy density reaches 65.4Wh kg-1The power density reaches 787.3W kg-1. The electrochemical energy storage characteristics are shown in fig. 4.
The embodiments are described in a progressive manner, each embodiment focuses on differences from other embodiments, and the same or similar parts among the embodiments are referred to each other. The device disclosed by the embodiment corresponds to the method disclosed by the embodiment, so that the description is simple, and the relevant points can be referred to the method part for description.
The preparation method and the application of the biomass porous carbon material based on the novel iodine simple substance pore-forming agent are described in detail above. The principles and embodiments of the present invention are explained herein using specific examples, which are presented only to assist in understanding the method and its core concepts. It should be noted that, for those skilled in the art, it is possible to make various improvements and modifications to the present invention without departing from the principle of the present invention, and those improvements and modifications also fall within the scope of the claims of the present invention.
Claims (5)
1. A preparation method of a biomass porous carbon material based on an iodine simple substance pore-forming agent is characterized by sequentially comprising the following steps:
s1: dissolving a carbon source in water; the carbon source is soluble starch,
s2: adding an iodine source into the solution obtained in the last step, heating to 90 ℃, and stirring for dissolving; the iodine source is iodine simple substance;
s3: adding tartaric acid into the mixed solution obtained in the last step, and stirring for dissolving;
s4: adding potassium nitrate into the mixed solution obtained in the last step, and stirring for dissolving;
s5: drying the mixed solution obtained in the last step at the temperature of 80-180 ℃ for 8-48 h;
s6: grinding the porous foamed solid obtained in the last step into powder, putting the powder into a quartz crucible, and carbonizing the powder at a temperature of 600-1200 ℃ at a heating rate of 2-20 ℃/min under the protection of inert atmosphere for 60-180 min;
s7: and (3) fully stirring the powder obtained in the last step in dilute acid, removing impurities in the carbon material by ultrasonic waves, washing the carbon material to be neutral by water, and drying the carbon material to obtain the porous carbon material.
2. The method for preparing the biomass porous carbon material based on the elemental iodine pore-forming agent as claimed in claim 1, wherein in step S6, the inert gas is argon or nitrogen.
3. The method for preparing the biomass porous carbon material based on the iodine simple substance pore former is characterized in that in the step S7, the dilute acid is 0.1-3M hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid or oxalic acid, the stirring treatment time is 0.5-6 h, the ultrasonic treatment time is 0.5-6 h, the oven temperature is 80-180 ℃, and the drying time is 8-48 h.
4. A biomass porous carbon material obtained by the production method according to claim 1.
5. The application of the biomass porous carbon material of claim 4 in electrochemical energy storage.
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